Defect evolution and photoluminescence in anion-defective alumina single crystals exposed to high doses of gamma-rays

A method of luminescent UV and VUV spectroscopy was used to study the evolution of color centers in anion-defective alumina single crystals exposed to high doses of gamma-radiation. A sharp drop in the intensity of the emission bands and, therefore, the concentration of F⁺ and F-centers associated with the formation of aggregate F₂-type centers was found. The aggregate centers create an additional emission band in the range of (1.8–2.8) eV. When the crystals are exposed to middle and high doses, the photoluminescence (PL) intensity is the highest in the emission band of F₂²⁺-centers, which indicates a high concentration of the aggregates from singly charged oxygen vacancies (of F⁺-centers). When PL of the crystals exposed to high doses is excited with synchrotron radiation of the VUV range, a wide emission band in the red and near infrared (NIR) regions is registered. The centers related presumably to impurity defects, their aggregates and clusters consisting of several oxygen vacancies are responsible for this emission band.     

Thermal- and photo-induced transformations of luminescence centers in αd-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> anion-defective crystals

The thermal- and photo-induced transformations of luminescence centers in anion-defective crystals of α-Al₂O₃ have been investigated. It has been found that the exposure of crystals to ultraviolet light at temperatures in the range 50–900°C leads to substantial changes in their thermoluminescence and radioluminescence spectra. According to the optical absorption and photoluminescence data, the detected F-type centers have been identified and the temperature ranges of the F → F ⁺ → F ₂ transformations and their possible mechanisms have been determined. The special attention has been drawn to the detailed similarity in the formation of complex F ₂-type centers in the initially perfect α-Al₂O₃ crystals irradiated with fast neutrons and in the studied anion-defective crystals.     

Luminescence properties of oxide coatings on aluminum alloys

This is a study of the luminescence properties of coatings formed on aluminum alloys by anodizing in electrolytic solutions based on oxalic, sulfuric, and tartaric-sulfonic acids. At least two emission centers, with band maxima in the ranges of 390–410 and 470–510 nm, can be reliably identified in the photoluminescence spectra. The first type of center is characterized by single-band photoluminescence excitation spectra and the second, by two-band spectra. An analysis of the two-band photoluminescence excitation (PLE) spectra in the range of 470–510 nm shows that the position of the narrow short-wavelength PLE spectrum near 272 nm is independent of the type of acid used in the anodization process. The position and shape of the other PLE spectral bands depend both on the type of acid used and on the processing of the alloy or alumina surfaces. It is assumed that defect-free alumina centers are responsible for the 272 nm PLE band, while the other photoluminescence bands are caused primarily by different divacancies of oxygen (F₂⁺ {F_2^+} , F ₂, and F₂⁺² {F_2^{+2}} centers) whose origin is governed by the type of electrolyte.     

Dependence of blue-emitting property on nanopore geometrical structure in Al-based porous anodic alumina membranes

Porous anodic alumina (PAA) membranes were fabricated using anodization of Al foils. Based on morphology observations and photoluminescence (PL) measurements, it is revealed that the peak position of the observed blue PL band has an evident dependence on nanopore geometrical structure. The blue PL band is asymmetrical and can be Gaussian divided into two subbands, which originate in two kinds of oxygen-deficient centers, F⁺ and F centers. On raising the anodic voltage, the two subbands red shift and the intensity of the subband from the F⁺ centers relative to that from the F centers increases. This suggests that the increases of nanopore size and porosity make partial F⁺ centers convert into F centers. The mechanism of this conversion is further discussed on the basis of the PL behavior of the PAA membrane under ultraviolet irradiation. This work will be beneficial to the better understanding of the PL property of the PAA membrane. PACS 78.55.-m; 82.45.Cc; 76.30.Mi     

Photoluminescence properties of anodic alumina membranes with ordered nanopore arrays

Photoluminescence (PL) of anodic alumina membranes (AAMs) with ordered nanopore arrays fabricated in oxalic acid has been investigated under different annealing temperatures. The PL intensity firstly increases, and at 500 °C reaches a maximum value, then decreases. The structural transition from amorphous to γ-Al₂O₃ in AAMs has been confirmed by X-ray diffraction. Thermogravimetric analysis results and electron paramagnetic resonance measurements revealed that the PL band of alumina membranes could be attributed to the oxygen-related defect centers (F⁺ centers) rather than the luminescent centers transformed from oxalic impurities.     

(OH)-离子对F2+心的稳定作用

基于我们的实验结果,本文讨论了(OH)^-离子在LiF晶体中对F₂⁺心的稳定作用,给出了样品在室温下放置九个月时,其中的F₂⁺心吸收峰,此时F₂⁺心仍达到实现激光振荡所要求的浓度。 关键词：     

Luminescence property studies of α-Al2O3 by means of nanosecond time-resolved VUV spectroscopy

The luminescence spectra of corundum monocrystals grown by different methods are investigated by means of a time-resolved spectroscopy method at temperatures 90 K and 300 K. The existence of fast and slow emission in the VUV luminescence spectra of irradiated and nonirradiated crystals was observed. We observed luminescence bands with a maximum at 326 nm produced by F ⁺ centers. A new type of fast luminescence at the band of 270 nm was found. This is known as cross-luminescence and is connected with the recombination of valence band electrons with the holes in the low ground band. It was shown that the band of 410 nm isn't due to to anionic centers (F-centers), but is determined by the short lifetime center of emission (F ^- -centers). Received 20 October 1998 and Received in final form 20 January 1999     

Mechanism of <Emphasis Type="Italic">F</Emphasis>-center luminescence in anion-defective aluminum oxide single crystals

New experimental data illustrating the effect of deep traps on the luminescence properties of anion-defective α-Al₂O₃ single crystals are presented. It was established that deep traps have electronic nature and their filling occurs through photoionization of F centers and is accompanied by F → F⁺-center conversion. Model concepts were developed that describe the luminescence mechanism in anion-defective aluminum oxide single crystals with inclusion of thermal ionization of the excited F-center states. The validity of the model was supported by experimental data obtained in a study of thermoluminescence, thermally stimulated exoelectron emission, and thermally stimulated electrical conductivity.     

Strong ultraviolet and violet photoluminescence from Si-based anodic porous alumina films

We have investigated photoluminescence (PL) from Si-based anodic porous alumina films formed by real-time controlled anodization of electron-beam evaporated Al films. As-anodized samples show three strong PL bands at 295, 340, and 395 nm. These bands blueshift and their intensities decrease after the samples are annealed. When the annealing temperature increases to 1000 °C, the blueshift becomes specially pronounced and meanwhile the structures of the films develop toward crystalline Al₂O₃. Based on discussions on the thermal annealing behaviors of the PL and PL excitation spectra, we suggest that optical transitions in oxygen-related defects, F⁺ (oxygen vacancy with one electron) centers, are responsible for the observed ultraviolet and violet PL. Received: 24 July 2000 / Accepted: 24 February 2001 / Published online: 3 May 2001     

Influence of electrolyte composition on photoluminescent properties of anodic aluminum oxide

Luminescent properties of anodic alumina fabricated in anodizing solutions containing oxalic, sulfuric, and phosphoric acids in addition to those modified by thermal annealing are investigated. Comparison of the obtained data shows that F⁺-centers are responsible for the luminescence band at 390 nm. The intense photoluminescence band of porous anodic alumina substrates at 450–500 nm is associated with oxalate anions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 208–212, March–April, 2008.     

The optical and paramagnetic absorption spectra of MgO:Mn single crystals irradiated in a reactor

The optical and paramagnetic absorption spectra of MgO:Mn crystals of different origin, irradiated in a reactor, have been investigated. It is found that, in spite of only a small amount of Mn²⁺ impurity ions in the investigated crystals, their influence on the efficiency of formation and accumulation of F⁺-centers is dominant. The dependence of the number of F⁺-centers both on irradiation dose and on manganese concentration is studied.     

Optical properties of alumina membranes prepared by anodic oxidation process

The luminescence property of anodic alumina membranes (AAMs) with ordered nanopore arrays prepared by electrochemically anodizing aluminum in oxalic acid solutions have been investigated. Photoluminescence emission (PL) measurement shows that a blue PL band occurs in the wavelength ranges of 300-600 nm. The PL intensity and peak position of AAMs depend markedly on the excitation wavelength. A new peak located at 518 nm can be observed under a monitoring wavelength at 429 nm in the photoluminescence excitation (PLE) spectra. Convincing evidences have been presented that the PLE would be associated with the residual aluminum ions in the membrane. The PLE and PL of AAMs, as a function of anodizing times, have been discussed. It is found that the oxalic impurities incorporated in the AAMs would have important influences on the optical properties of AAMs in the initial stage of anodization. The PL and PLE spectra obtained show that there are three optical centers, of which the first is originated from the F⁺ centers in AAMs, the second is correlated with the oxalic impurities incorporated in the AAMs, and the third is associated with the excess aluminum ions in the membrane.     

On the theory of the molecular states of <Emphasis Type="Italic">A</Emphasis><Superscript>+</Superscript>-centers in semiconductor quantum wells

The spectra of photoluminescence in the GaAs/AlGaAs quantum wells with A ₂⁺-centers are calculated within the model of the zero radius potential. It is shown that the model of A ₂⁺-centers can adequately describe the experimental data that point to the existence of molecular states of A ⁺-centers in 2D GaAs/AlGaAs structures.     

Photoluminescence spectra of nitrogen implanted GaSe crystals

GaSe single crystals were N-implanted along c-axis with ion beams of 10¹⁴ and 10¹⁶ ions/cm² doses having energy values of 60 and 100 keV. The photoluminescence (PL) spectra of undoped and N-implanted GaSe crystals were measured at different temperatures. The PL intensity was observed to decrease with increasing implantation dose while the FWHM of the exciton peaks increased. In heavily doped crystals, due to the interaction with the radiation induced disorders, the wave vector selection rules are satisfied and an indirect exciton PL band is observed 36 meV below the direct exciton states.     

Luminescence of CsBr:Eu films grown by liquid-phase epitaxy

By liquid-phase epitaxy from an aqueous alcoholic solution, we have obtained films of the well-known storage phospor CsBr:Eu, and we have studied their cathodoluminescence and photoluminescence (PL) spectra compared with the undoped CsBr films. We have established that the structure of the photoluminescence centers of the CsBr:Eu films when excited by laser radiation in the absorption band of the Eu²⁺ ions (λ = 337 nm) includes Eu²⁺-V_Cs isolated dipole centers and CsEuBr₃ aggregate centers, and also luminescence centers based on inclusions of hydroxyl group OH⁻ with the corresponding emission bands in the 440 nm, 520 nm, and 600 nm regions. We have studied the dependence of the spectra and the intensity of the photoluminescence for CsBr:Eu films on annealing temperature in air at 423–483 K, compared with analogous dependences for CsBr:Eu single crystals obtained from the melt. We have shown that annealing the films at T = 423–463 K leads to rapid formation of CsEuBr3 aggregate luminescence centers, while for T > 473 K thermal degradation of these centers occurs. We conclude that the observed differences between the photoluminescence spectra of CsBr:Eu films and CsBr:Eu single crystals may be due to additional doping of the films with OH⁻ ions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 191–194, March–April, 2006.     

LiF晶体F3+色心的实验研究

本文从实验上系统地研究了在不同条件下电子束辐照LiF晶体所形成的F₃⁺色心的光学特点。并且由荧光光谱分析了F₃⁺心和F₂心,的相对密度关系。实验表明,辐照温度对于色心的形成和密度的相对大小起着关键的作用。主要实验结果包括:1)在液氮温度下辐照,然后在暗处加热至室温可形成高密度的F₃⁺心,表现在发射光谱中F₃⁺心荧光占绝对优势。吸收光谱表明没有N心和R心。2)由动力学荧光谱可以看到低温辐照的样品在F₂⁺心衰变的同时,F₃⁺心密度迅速增加。而室温辐照的样品则是F₂心,与F₃⁺心的密度以近似相等的速率增加。3)详细观察了F₃⁺心530nm荧光激发带与F₂心670nm荧光激发带半宽度的变化和双峰结构。由此对M吸收区的发光特点作了解释。 关键词：     

Lithium fluoride colour centres-based imaging detectors for proton beam characterization at high doses

Proton beams of 7 MeV energy, produced by a linear accelerator, were used to irradiate LiF crystals and thin films thermally evaporated on glass substrates in the dose range from 10³ to 4 × 10⁶ Gy, inducing the formation of stable photoluminescent colour centres (mainly F₂ and F₃⁺), emitting in the visible spectral range. Using a conventional fluorescence microscope, the transversal proton beam intensity was mapped by acquiring the photoluminescence image of the irradiated spots. Image analysis allowed measuring the integrated photoluminescence intensity as a function of the irradiation dose: a linear optical response was obtained up to different maximum dose values, after which a quenching was observed, depending on the nature of the samples (crystals or films). The colour centres formation was investigated by optical absorption spectroscopy at room temperature and the Principal Component Analysis was applied to the absorption spectra of irradiated LiF crystals. In samples irradiated at highest doses, it allowed clearly identifying the formation of more complex aggregate defects, which appears strictly related to the observed photoluminescence quenching effect.     

Photoluminescence of f-centers in films of anodic alumina

Results are reported from a study of the optical properties of porous alumina films obtained by anodizing in a water solution of sulfuric acid and modified by thermal annealing in air at T ≥ 850°C. A comparative analysis of the data shows that the near-UV and visible photoluminescence of alumina anodized in a sulfuric acid solution is caused primarily by oxygen divacancies (F₂, F₂⁺ _2^{+} , and F₂^{2 +} _2^{2 + } centers), while sulfate ions have little effect on the luminescence properties of anodic alumina in this spectral range.     

Photoluminescence investigations of cubic boron nitride doped with neodymium during high-pressure synthesis

Micropowders of cubic boron nitride doped with neodymium are prepared under high-pressure and high-temperature conditions. The phase composition of the micropowders is studied using X-ray diffractometry and X-ray fluorescence analysis. The photoluminescence, photoluminescence excitation spectra, and the life-time of the ⁴ F _3/2 excited state of Nd ions introduced into cubic boron nitride are investigated. In photoluminescence spectra of the micropowders, structured bands are recorded in the range of the ⁴ F _3/2 → ⁴ I _9/2 and ⁴ F _3/2 → ⁴ I _11/2 electronic transitions. A higher intensity of the first structured band indicates that the corresponding photoluminescence in cubic boron nitride doped with neodymium is excited by the “three-level scheme.” It is demonstrated that an increase in the concentration of the neodymium compound in the growth batch leads to the formation of two luminescence centers Nd1 and Nd2 formed by neodymium ions located in different low-symmetry crystal fields in the micropowders. This is confirmed by X-ray diffraction investigations and the study of the photoluminescence decay curves. The ⁴ F _3/2 short-lived state is assigned to the Nd ions forming the Nd1 centers, and the long-lived state is attributed to the Nd ions forming the Nd2 centers.